CN114703377A - Method for extracting copper from acidic etching waste liquid - Google Patents
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Abstract
The invention relates to the technical field of wastewater treatment and resource recovery, and discloses a method for extracting copper from acidic etching waste liquid, which comprises the following steps: the method comprises the following steps: extracting the acidic etching waste liquid by using TBP to obtain a TBP loaded organic phase and an extracted water phase; step two: back extracting TBP loaded organic phase with water to obtain copper chloride solution containing hydrochloric acid; step three: performing secondary extraction on the extraction water phase by using P204 to obtain a P204 loaded organic phase; step four: and (3) back-extracting the P204 loaded organic phase by using a copper chloride solution obtained by back-extracting the TBP to obtain an enriched copper chloride solution. The concentration of the copper in the extracted water phase after two-step extraction can be reduced to below 50ppm, the copper recovery rate reaches above 99.9%, and the copper in the acidic etching waste liquid is completely recovered. The method organically integrates the characteristics of the two-step extraction, has complementary advantages, effectively reduces the consumption of reagents, realizes the purposes of treating the acidic etching waste liquid at low cost and completely recovering copper resources, and has green and environment-friendly treatment process.
Description
Technical Field
The invention relates to the technical field of wastewater treatment and resource recovery, in particular to a method for extracting copper from acidic etching waste liquid.
Background
In a factory for producing circuit boards by adopting an acid etching technology, the acid etching solution can be recycled for a long time to cause the etching performance to be reduced and cannot be used continuously, so that a large amount of acid etching waste liquid generated in the factory for etching the circuit boards needs to be discharged for treatment. The copper concentration in the acidic etching waste liquid is often up to more than 100g/L, and the acidic etching waste liquid has high utilization value, but the treatment of the acidic etching waste liquid becomes a big problem for a plurality of enterprises for etching circuit boards because the treatment cost of the acidic etching waste liquid is high and the environmental protection pressure is huge.
At present, the industrial treatment method of the acidic etching waste liquid mainly comprises a neutralization precipitation method, an extraction method and an electrochemical method. The neutralization precipitation method obtains copper hydroxide solid after neutralization with alkali, and then the copper hydroxide solid is dissolved by acid so as to further produce high-quality copper products. The method has the disadvantages of large alkali consumption, large wastewater quantity and high cost, and many factories have to treat the acidic etching solution without cost in order to relieve the environmental protection pressure. In the extraction method, a hydroxim extractant is used for directly extracting copper from an acidic etching solution, but the acidic etching solution contains hydrochloric acid with higher concentration, so that the hydroxim extractant has poor copper extraction effect, the stability of the extractant in a hydrochloric acid system is poor, the loss of the extractant is large, and the problem of serious entrainment exists in the extraction process. The other process in the extraction method is to adjust the pH value of the etching solution and then extract the etching solution, hydrochloric acid in the etching solution cannot be utilized in the method, and precipitates are generated in the neutralization process, so that the extraction operation is not facilitated. The electrochemical method for treating acidic waste etching solution is generally used for etching solution regeneration, and the acidic waste etching solution after electrochemical regeneration can be returned to the etching process for recycling after being properly adjusted, but when the acidic waste etching solution discharged outside is treated, the method has many limitations, such as easy generation of chlorine gas, low current efficiency, low copper recovery rate, low cathode copper quality and the like, and the waste etching solution after electrodeposition contains more copper and high-concentration acid and needs to be further treated for discharge, so that many disadvantages exist, and therefore, the development of a method for treating the acidic waste etching solution at low cost and completely recovering the copper therein is urgently needed.
Disclosure of Invention
The invention aims to provide a method for extracting copper from acidic etching waste liquid, which aims to solve the problems of high cost, high pollution, low comprehensive utilization rate of resources and the like in the acidic etching waste liquid treatment.
In order to achieve the purpose, the invention adopts the following technical scheme: a method for extracting copper from acidic etching waste liquid comprises the following steps:
the method comprises the following steps: extracting the acidic etching waste liquid by using TBP to obtain a TBP loaded organic phase and an extracted water phase;
step two: back extracting TBP loaded organic phase with water to obtain copper chloride solution containing hydrochloric acid;
step three: performing secondary extraction on the raffinate water phase by using P204 to obtain a P204 loaded organic phase;
step four: and (3) back-extracting the P204 loaded organic phase by using a copper chloride solution obtained by back-extracting the TBP to obtain an enriched copper chloride solution.
The principle and the advantages of the scheme are as follows: in practical application, in the technical scheme, aiming at the defects of copper extraction from the acidic etching waste liquid in the prior art, the inventor optimizes the extraction mode, reduces the copper concentration of the acidic etching waste liquid from about 100-120 g/L to below 0.05g/L by adopting two-step extraction, and ensures that the copper recovery rate is more than 99.9 percent. The two-step extraction method organically combines the characteristics of copper extraction by the two extracting agents, and the advantages of the two extracting agents are complemented by optimizing the extraction process, so that the consumption of the reagents is reduced, and the production cost is reduced. In the process, the optimization and matching of the types of the extracting agents are a big difficulty of the scheme, and the inventor tries ways of joint extraction of CLX50 and P204 (dioctyl phosphate), joint extraction of Lix984N and P204, single TBP (tributyl phosphate) extraction or single P204 extraction, and the like, and the result shows that emulsification and a large amount of flocculates occur when CLX50 extracts the acidic etching solution, the entrainment is serious, the obtained copper chloride product has low purity, the loss of the extracting agents is large, and the cost is high. When the Lix984N is used for extracting copper in the acidic etching solution, alkali needs to be added for neutralization to realize effective extraction of the copper, the alkali consumption is basically the same as that of the extraction only by using P204, and the Lix984N has the advantages of high degradation speed in the presence of hydrochloric acid, large loss of an extracting agent, difficulty in long-term stable operation and high operation cost. Through a plurality of exploration and trial, the TBP and the P204 combined extraction acidic etching solution has good complementary characteristics, and can effectively reduce the consumption of reagents.
In the first extraction step, a certain amount of hydrochloric acid can be extracted while extracting copper chloride by TBP, a copper chloride solution containing a certain amount of hydrochloric acid can be obtained after back extraction by water, and the copper chloride solution can be used as a back extraction solution of a P204 copper-carrying organic phase in the second step, so that the back extraction of copper can be realized almost without additionally adding acid or only adding a small amount of acid. Meanwhile, a certain amount of hydrochloric acid is extracted during copper extraction by the TBP, so that favorable conditions are created for deep copper extraction by the P204 in the second step, and the alkali consumption is effectively reduced. On the other hand, the copper chloride solution obtained by the back extraction of the second step P204 can return a part of the copper chloride solution to be used as the back extraction solution of the first step TBP due to the reduction of acidity, so that the back extraction efficiency of the first step TBP organic phase can be improved, the copper chloride is circularly enriched, and favorable conditions are created for the preparation of copper chloride products. In the scheme, organic combination is realized by two-step extraction, and the advantages are complementary; the process is simple, the used equipment is conventional extraction equipment, the cost is low, the operation is simple and convenient, the treatment scale can be large or small, and the method is suitable for various factories.
Preferably, as an improvement, in the step one, the mass concentration of TBP is 10-50%, the extraction time is 3-10min, the extraction stages are 3-6 stages, and the extraction mode is cross-flow extraction or countercurrent extraction.
In the technical scheme, in the extraction process, the concentration of an extracting agent, the extraction time and the extraction process (the number of stages) influence the extraction effect and the reagent consumption to a certain extent. The concentration of TBP has great influence on the extraction effect, too high concentration of TBP can cause difficult phase splitting, and too low concentration of TBP can cause insufficient extraction capability and influence the extraction effect; by combining the optimization of extraction time and extraction stages, the amount of front-end first-stage extracted copper can be ensured, the extraction burden of subsequent P204 is reduced, and the reagent consumption of acid and alkali can be reduced while the extraction effect is ensured.
Preferably, as an improvement, in the first step, the mass concentration of TBP is 20-45%, and the extraction ratio of each stage of extraction is 2-2.5: 1.
In the technical scheme, the concentration of TBP has great influence on the extraction effect, too high concentration of TBP can cause difficult phase separation, and too low concentration of TBP can cause insufficient extraction capability and influence the extraction effect; the extraction phase ratio has important influence on the extraction rate and extraction operation, the mixing effect and the phase separation effect are influenced when the extraction ratio is too large, the extraction rate is reduced when the extraction ratio is too small, and the above conditions are the preferable conditions verified by practice.
Preferably, as an improvement, in the step one, phase separation is performed after extraction to obtain a TBP loaded organic phase and an extracted aqueous phase, and the phase separation time is 5-20 min.
In the technical scheme, the effect of separating the TBP loaded organic phase from the raffinate aqueous phase can be ensured by optimizing the phase separation time, and the separation time is a better time range verified by practice.
Preferably, as an improvement, in the second step, the stripping time of the water and the TBP loaded organic phase is 3-10min, and the stripping ratio is 1-10: 1.
In the technical scheme, the back extraction time and the back extraction ratio have important influence on the back extraction effect, the back extraction efficiency is reduced if the back extraction time and the back extraction ratio are not proper, and the parameter range is a better range verified by practice.
Preferably, as an improvement, in the third step, the mass concentration of the P204 is 10-40%, the extraction time is 3-10min, and the extraction equilibrium pH is 3.5-4.5.
In the technical scheme, the concentration of P204 has a great influence on the extraction effect, the excessive concentration of P204 can cause difficult phase separation and increased entrainment, and the excessive concentration of P204 can cause the reduction of the copper extraction rate and finally the reduction of the copper recovery rate; the extraction time has direct influence on the extraction effect, and the extraction efficiency is reduced due to the excessively short extraction time. The extraction pH also has a great influence on the extraction effect, if the pH is too low, the copper extraction is incomplete, and if the pH is too high, the reagent consumption is increased, and the problem of difficult phase separation is possibly caused, wherein the pH range is a better range verified by practice.
Preferably, as a refinement, the mass concentration of P204 is from 20 to 30%.
In the technical scheme, experiments prove that when the mass concentration of the P204 is 20-30%, a relatively better extraction effect can be obtained, and further the recovery rate of copper is ensured.
Preferably, as an improvement, in the third step, the extraction ratio is 2.5-3: 1.
In the technical scheme, when the extraction ratio is 2.5-3:1, the extraction effect can be ensured, and unnecessary waste can be avoided.
Preferably, as an improvement, in the fourth step, the volume ratio of the P204 organic phase to the copper chloride solution is 1-5: 1.
In the technical scheme, the back extraction effect can be ensured within the range of the back extraction ratio.
Preferably, as an improvement, in the fourth step, part of the enriched copper chloride solution is returned to the second step to be used as a back extraction water phase of TBP; the stripped TBP and P204 are used to extract new acidic spent etching solution.
In the technical scheme, by the operation, the recycling of the enriched copper chloride can be realized, and the recycling of the extracting agents TBP and P204 can be realized by back extraction, so that the actual consumption is greatly reduced, and the aim of treating the acidic etching waste liquid with low cost and environmental protection is fulfilled.
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FIG. 1 is a flow chart of the present invention for extracting copper from acidic etching waste liquid.
Detailed Description
The following is a detailed description of the embodiments, but the embodiments of the present invention are not limited thereto. Unless otherwise specified, the technical means used in the following embodiments are conventional means well known to those skilled in the art; the experimental methods used are all conventional methods; the materials, reagents and the like used are all commercially available.
Example 1
The components of the acidic etching waste liquid to be treated are as follows: cu 123g/L, NaCl about 110g/L, NH4Cl about 30g/L, HCl 92 g/L.
As shown in fig. 1, a method for extracting copper from acidic etching waste liquid comprises the following steps:
step one, primary extraction: extracting the acidic etching waste liquid by using TBP with the concentration of 40 percent, wherein the extraction process is 6-stage cross-flow extraction, the phase ratio (volume ratio of organic phase to aqueous phase) of each stage of extraction is 2:1, and the single-stage extraction mixing time is 5 min; after the primary extraction is finished, carrying out phase separation to obtain an extracted water phase and a TBP loaded organic phase;
step two, primary back extraction: combining all levels of TBP loaded organic phases, and performing 2 levels of counter-current back extraction by using water, wherein the back extraction phase ratio (the volume ratio of an organic phase to an aqueous phase) is 6:1, so as to obtain a copper chloride solution containing a certain amount of hydrochloric acid;
step three, secondary extraction: carrying out deep copper extraction on the raffinate water phase by using 30% P204, wherein the extraction ratio is 2.5:1, the extraction process is 2-stage cross-flow extraction, the extraction equilibrium pH is 4.2, the extraction mixing time is 3min, a P204 loaded organic phase and raffinate are obtained after phase separation, and the copper content of the raffinate is 0.037 g/L;
step four, secondary back extraction: carrying out organic phase synthesis and back extraction on the P204 load, wherein a back extraction solution is the copper chloride solution obtained in the second step, and a small amount of hydrochloric acid is supplemented to obtain a copper chloride solution containing 59.7g/L of copper; wherein, the total amount of other impurity metal ions is less than 50ppm, the pH value is 1.6, and the copper recovery rate is more than 99.9 percent.
Example 2
The composition of a certain acidic etching waste liquid to be treated is as follows: cu 102g/L, NaCl about 70g/L, NH4Cl about 80g/L, and HCl 90 g/L.
A method for extracting copper from acidic etching waste liquid comprises the following steps:
step one, primary extraction: extracting the acidic etching waste liquid by using TBP with the concentration of 35%, wherein the extraction process is 5-stage cross-flow extraction, the ratio of extraction phase (volume ratio of organic phase to aqueous phase) of each stage is 2:1, and the single-stage extraction mixing time is 5 min; after the primary extraction is finished, carrying out phase separation to obtain an extracted water phase and a TBP loaded organic phase;
step two, primary back extraction: combining all levels of TBP loaded organic phases, and performing 2 levels of counter-current back extraction by using water, wherein the back extraction phase ratio (the volume ratio of an organic phase to an aqueous phase) is 6:1, so as to obtain a copper chloride solution containing a certain amount of hydrochloric acid;
step three, secondary extraction: carrying out deep copper extraction on the raffinate water phase by using 25% P204, wherein the extraction ratio is 2.5:1, the extraction process is 2-stage cross-flow extraction, the extraction equilibrium pH is 4.3, the extraction mixing time is 3min, a P204 loaded organic phase and raffinate are obtained after phase separation, and the copper content of the raffinate is 0.035 g/L;
step four, secondary back extraction: carrying out organic phase synthesis and back extraction on the P204 load, wherein the back extraction solution is the copper chloride solution obtained in the second step, and a small amount of hydrochloric acid is supplemented to obtain a copper chloride solution containing 60.7g/L copper; wherein, the total amount of other impurity metal ions is less than 50ppm, the pH value is 1.7, and the copper recovery rate is more than 99.9 percent.
Example 3
In this example, the acid etching waste liquid is the same as that in the above example 2, and another scheme is designed to increase the concentration of the copper chloride mother liquor, which is different from that in example 2 in that: the stripping aqueous phase of the TBP loaded organic phase is water and a part of copper chloride solution obtained after stripping P204, the volume ratio of the water to the copper chloride solution is 2:1, and the rest of the process is the same as that of the example 2. The results were as follows: the final raffinate contains 0.035g/L of copper, and the copper recovery rate is more than 99.9%; the copper chloride solution finally obtained contains 80.6g/L of copper, wherein the total content of impurity metal ions is less than 50ppm, and the pH value is 1.7.
Example 4
The composition of a certain acidic etching waste liquid to be treated is as follows: cu 90g/L, NaCl about 110g/L, NH4Cl about 40g/L, HCl 94 g/L.
A method for extracting copper from acidic etching waste liquid comprises the following steps:
step one, primary extraction: extracting the acidic etching waste liquid by using TBP with the concentration of 40 percent, wherein the extraction process is 4-stage cross-flow extraction, the phase ratio (volume ratio of organic phase to aqueous phase) of each stage of extraction is 2.5:1, and the single-stage extraction mixing time is 10 min; after the primary extraction is finished, carrying out phase separation to obtain an extracted water phase and a TBP loaded organic phase;
step two, primary back extraction: combining all levels of TBP loaded organic phases, and performing 2 levels of counter-current back extraction by using water, wherein the back extraction phase ratio (volume ratio of organic phase to aqueous phase) is 3:1, so as to obtain a copper chloride solution containing a certain amount of hydrochloric acid;
step three, secondary extraction: carrying out deep copper extraction on the raffinate water phase by using 30% P204, wherein the extraction ratio is 3:1, the extraction process is 2-stage cross-flow extraction, the extraction equilibrium pH is 4.3, the extraction mixing time is 4min, a P204 loaded organic phase and raffinate are obtained after phase separation, and the copper content of the raffinate is 0.045 g/L;
step four, secondary back extraction: and (3) carrying out organic phase synthesis and back extraction on the P204 load, wherein a back extraction solution is the copper chloride solution obtained in the second step, a small amount of hydrochloric acid is supplemented to obtain a copper chloride solution containing 27.2g/L of copper, the pH value is 1.7, the obtained copper chloride solution is completely returned to be used as a back extraction solution of TBP in the next extraction cycle to enrich the copper, the cycle is carried out for 3 times, and the copper chloride solution containing 81.5g/L of copper, the pH value is 1.7, the total amount of impurity metal ions is less than 90ppm, and the copper recovery rate is 99.9%.
Example 5
The composition of a certain acidic etching waste liquid to be treated is as follows: cu 105g/L, NaCl about 100g/L, NH4Cl about 45g/L, and HCl 85 g/L.
A method for extracting copper from acidic etching waste liquid comprises the following steps:
step one, primary extraction: firstly extracting the acidic etching waste liquid by using TBP with the concentration of 45%, wherein the extraction process is 3-stage cross-flow extraction, the ratio of extraction phase (volume ratio of organic phase to aqueous phase) of each stage is 2.5:1, and the single-stage extraction mixing time is 5 min; after the primary extraction is finished, carrying out phase separation to obtain an extracted water phase and a TBP loaded organic phase;
step two, primary back extraction: combining all levels of TBP loaded organic phases, and performing 1-level countercurrent back extraction by using water, wherein the back extraction phase ratio (the volume ratio of an organic phase to an aqueous phase) is 4:1, so as to obtain a copper chloride solution containing a certain amount of hydrochloric acid;
step three, secondary extraction: carrying out deep copper extraction on the raffinate water phase by using 28% P204, wherein the extraction ratio is 4:1, the extraction process is 3-level countercurrent extraction, the extraction equilibrium pH is 4.0, the extraction mixing time is 5min, a P204 loaded organic phase and raffinate are obtained after phase separation, and the copper content of the raffinate is 0.014 g/L;
step four, secondary back extraction: carrying out organic phase synthesis and back extraction on the P204 load, wherein a back extraction solution is the copper chloride solution obtained in the second step, and a small amount of hydrochloric acid is supplemented to obtain a copper chloride solution containing 54.5g/L of copper, and the pH value is 1.7; wherein, the total amount of other impurity metal ions is less than 50ppm, and the copper recovery rate is more than 99.9%.
Comparative example 1
The components of the acidic etching waste liquid to be treated are as follows: cu 123g/L, NaCl about 110g/L, NH4Cl about 30g/L, HCl 92 g/L.
The difference between this comparative example and example 1 is that in this comparative example, only TBP was used to extract copper, P204 extraction was omitted, and the number of TBP extraction stages was increased to 8 stages (cross-flow extraction), the extraction ratio was still 2:1, and the stripping ratio was 10:1, two stages of counter-current stripping were performed, each group was subjected to 3 replicates, and the Cu concentration was measured by atomic absorption spectroscopy (the same below), and the results are shown in table 1.
TABLE 1 comparison of "TBP + P204" with the extraction index of the TBP Process
From the data in table 1, the copper recovery of example 1 (i.e., using the TBP and P204 two-step extraction process) is higher than that of comparative example 1 (extracted with TBP only), with the copper being substantially completely recovered in example 1 and only 47.1% in comparative example 1. By contrast, the synergistic extraction with TBP and P204 has a clear advantage in copper recovery.
Comparative example 2
The composition of a certain acidic etching waste liquid to be treated is as follows: cu 123g/L, NaCl about 110g/L, NH4Cl about 30g/L, HCl 92 g/L.
The difference between the comparative example and the example 1 is that in the comparative example, only P204 is used for extracting copper, TBP extraction is cancelled, sodium hydroxide is used for adjusting the pH value of the etching waste liquid to 1.5 before copper extraction is carried out, the P204 extraction process is 4-stage cross-flow extraction, the extraction ratio is 2.5:1, sodium hydroxide solution is used for adjusting the balance pH value to 4.2, the concentration of P204 is 30%, the loaded organic phases obtained by 4-stage extraction are combined and subjected to back extraction after the extraction is finished, the back extraction ratio is 5:1, and the back extraction process is two-stage counter-flow back extraction. Each group was subjected to 3 replicates and the copper recovery and reagent consumption are shown in table 2.
TABLE 2 index and reagent consumption comparison of "TBP + P204" Process with P204 Process
From the data in table 2, the copper recovery rate of the "TBP + P204" two-step extraction process is equivalent to that of the pure P204 process, and basically the copper can be completely recovered, but the alkali consumption and the acid consumption of the pure P204 extraction process are much higher than those of the "TBP + P204" process, because when the pure P204 process is adopted, more alkali needs to be consumed in the neutralization of the acidic etching solution and the extraction process, and more acid needs to be added in the stripping process to strip the copper. By comparison, the "TBP + P204" two-step extraction process has significant advantages in terms of reagent consumption.
Comparative examples 3-6 differ from example 1 only in part of the actual selection and parameter settings, and the specific test design and test results are detailed in table 3. Note: the components of the acidic etching waste liquid to be treated are as follows: cu 123g/L, NaCl about 110g/L, NH4Cl about 30g/L, and HCl 92 g/L.
TABLE 3
Note: in comparative example 4, the stripping solution used for stripping Lix984N was 2N HCl solution.
The results show that: CLX50 is used for replacing TBP to carry out synergistic extraction with P204, so that higher purity of copper chloride can be ensured, but the consumption of alkali is increased by 30% compared with that of example 1, and the consumption of acid is increased by 50% compared with that of example 1. Lix984N was used to replace TBP and to perform synergistic extraction with P204, resulting in a higher copper concentration in the raffinate, incomplete extraction and more than twice the acid and base consumption as in example 1. In addition, CLX50 and Lix984N separate extraction experiments are carried out, and the results show that: when CLX50 is used for extracting the acidic etching solution independently, the extraction effect is poor, emulsification and a large amount of flocculates can occur, the entrainment is serious, the loss of the extracting agent is large, the purity of the obtained copper chloride product is low, and the production cost is high. When Lix984N is used for extracting copper from the acidic etching solution alone, the copper extraction rate is very low, and the recovery rate is only 12.2%.
The foregoing is merely an example of the present invention and common general knowledge in the art of designing and/or characterizing particular aspects and/or features is not described in any greater detail herein. It should be noted that, for those skilled in the art, without departing from the technical solution of the present invention, several variations and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (10)
1. A method for extracting copper from acidic etching waste liquid is characterized by comprising the following steps:
the method comprises the following steps: extracting the acidic etching waste liquid by using TBP to obtain a TBP loaded organic phase and an extracted water phase;
step two: back extracting TBP loaded organic phase with water to obtain copper chloride solution containing hydrochloric acid;
step three: performing secondary extraction on the raffinate water phase by using P204 to obtain a P204 loaded organic phase;
step four: and (3) back-extracting the P204 loaded organic phase by using a copper chloride solution obtained by back-extracting the TBP to obtain an enriched copper chloride solution.
2. A method of extracting copper from acidic etching waste liquid according to claim 1, characterized in that: in the first step, the mass concentration of TBP is 10-50%, the extraction time is 3-10min, the extraction stage number is 3-6, and the extraction mode is cross-flow extraction or counter-flow extraction.
3. A method according to claim 2, characterized in that: in the first step, the mass concentration of TBP is 20-45%, and the extraction ratio of each stage of extraction is 2-2.5: 1.
4. A method according to claim 3, characterized in that: in the first step, phase separation is carried out after extraction to obtain a TBP loaded organic phase and an extracted water phase, and the phase separation time is 5-20 min.
5. A method according to claim 4, characterized in that: in the second step, the back extraction time of the water and the TBP loaded organic phase is 3-10min, and the back extraction ratio is 1-10: 1.
6. A method according to claim 5, characterized in that: in the third step, the mass concentration of P204 is 10-40%, the extraction time is 3-10min, and the extraction equilibrium pH is 3.5-4.5.
7. A method of extracting copper from acidic etching waste liquid according to claim 6, characterized in that: the mass concentration of the P204 is 20-30%.
8. A method according to claim 7, characterized in that: in the third step, the extraction ratio is 2.5-3: 1.
9. A method according to claim 8, characterized in that: in the fourth step, the volume ratio of the P204 organic phase to the copper chloride solution is 1-5: 1.
10. A method according to claim 9 for extracting copper from acidic etching waste liquid, characterized in that: in the fourth step, part of the enriched copper chloride solution returns to the second step to be used as a back extraction water phase of TBP; the stripped TBP and P204 are used for extracting new acidic waste etching solution.
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